JPH08190178A - Solid processing agent for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To prevent occurrence of the sticking phenomenon of the solid processing agent across rollers and to enable a stable fixing performance to be held and to obtain good preservability during storage even under high temperature conditions for a long period by incorporating a thiosulfate and at least one kind of specified compound in the processing agent. CONSTITUTION: The processing agent contains the thiosulfate and at least one kind of the compounds represented by formulae comprising I and II in which Q is an atomic group necessary to form an N-containing hetero ring; R1 is an H atom or a 1-6 C alkyl or cycloalkyl group or an aryl or heterocyclic group or an amino group or each of them may be substituted; each of R2 and R3 is an H atom or a 1-6 C alkyl group or an amino group or a 1-3 C acyl group or an aryl or alkenyl group or the like; A is a group of formula III or an n1 -valent heterocyclic group; each of X and X' is =S, =O, or =NR''; and each of R and R' is the same as R2 and R3 .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for silver halide photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) (hereinafter also simply referred to as solid processing agents), and more specifically to the preservability of the solid processing agents. And a solid processing agent for silver halide photographic light-sensitive materials having excellent solubility.

[0002]

2. Description of the Related Art In recent years, solidification of a processing agent for silver halide photographic light-sensitive materials has been studied from the viewpoints of environmental friendliness and reduction of replenisher preparation work load. For example, JP-A-5-119454.
JP-A-5-165174 and JP-A-5-232656 each disclose a technique in which a solid thiosulfate-containing treatment agent is directly supplied with fixing ability.

[0003]

Certainly, the technique described in the above patent makes it possible to reduce the use of the conventional polybin for containing the liquid replenisher (kit) and the work load for producing the replenisher. It has been found that alone cannot solve the problems shown below.

First, the above-mentioned patent describes an embodiment in which the fixing processing time of the color negative film is 90 seconds. Usually, in order to achieve such a quick fixing processing, It is necessary to raise the thiosulfate concentration of the above to some extent. If the concentration of thiosulfate is increased, it will be treated especially when neglecting to wash the transition roller part of the first fixing tank to the second fixing tank or the fixing tank to the next tank (stabilizing tank or washing tank) every day. Due to the photosensitive material, the fixing droplets that have adhered to the crossover roller section are dried and air-oxidized to decompose thiosulfate to generate a hydrophobic substance, which easily causes a problem that a strong hydrophobic bond (fixing) occurs with the roller surface. Of. When this sticking phenomenon occurs,
This may cause irreversible problems such as scratches on the photosensitive material that is being conveyed.

The relationship between the concentration of thiosulfate in the processing solution and the fixing performance will be described. The fixing performance increases as the concentration of thiosulfate increases up to a certain concentration, but the concentration of thiosulfate increases to a certain level. On the contrary, it has been found that the fixing performance is deteriorated by the above. The concentration of thiosulfate in the processing solution for achieving the above-mentioned rapid fixing processing corresponds to the concentration in this critical region. For example, in the case where the amount of the photosensitive material processed per day is small, the processing solution is The concentration of the processing liquid tends to concentrate due to the evaporation of the solvent, and the concentration of thiosulfate in the processing liquid increases due to the concentration, which causes a problem that the fixing performance deteriorates. Furthermore, when such a concentrated treatment liquid is left under low temperature conditions (for example, assuming that it is not operating in winter), crystals of thiosulfate are precipitated and grown in the treatment liquid, It was found that the circulation performance is hindered and the fixing performance is further deteriorated by reducing the effective thiosulfate in the processing liquid.

Further, assuming a case where the solid treating agent is stored on the deck for a long period of time during transportation of the solid treating agent by a ship, the solid treating agent contains a thiosulfate under such a high temperature long term storage condition. In the case of solid processing agents for fixing and bleach-fixing, yellow insoluble sulfides, which are considered to be decomposition products of thiosulfate, are produced, and these insoluble sulfides adhere to the filters in the fixing and bleach-fixing treatment layers. It has also been found that the clogging of the filter causes the poor circulation of the processing solution to cause the deterioration of the photographic performance, and the sulfide adheres to the processed light-sensitive material to significantly reduce the commercial value.

When the solid processing agent is in the form of granules or tablets, when the thiosulfate is decomposed to form a sulfide,
The binding force between the components existing around the sulfide is likely to decrease, and the powder of the solid processing agent due to vibration and friction becomes more intense.

The object of the present invention is, first of all, to prevent the fixing phenomenon of the transition roller portion and to maintain a stable fixing processing performance even when the processing amount of the photosensitive material per day is small. The second object is to provide a solid processing agent for silver photographic light-sensitive materials, and secondly, to provide a solid processing agent for silver halide photographic light-sensitive materials having good preservability even under high temperature long-term storage conditions.

[0009]

The above-mentioned object of the present invention can be achieved by the following constitutions.

[0010] 1. A solid processing agent for a silver halide photographic light-sensitive material, which is directly supplied to a processing solution for a silver halide photographic light-sensitive material having fixing ability, contains a thiosulfate and has the following general formulas [I], [II], [ A solid processing agent for a silver halide photographic light-sensitive material, comprising at least one compound selected from III], [IV] and [V].

[0011]

[Chemical 10]

In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or the number of carbon atoms. It represents 1 to 6 substituted or unsubstituted alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (including those in which 5- to 6-membered unsaturated rings are fused), or amino groups.

[0013]

[Chemical 11]

In the formula, R ₂ and R ₃ are each a hydrogen atom,
It represents an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. A is

[0015]

[Chemical 12]

Or an n ₁ -valent heterocyclic residue (including a condensed 5- or 6-membered unsaturated ring), X is = S,
Represents ═O or ═NR ″, where R and R ′ are synonymous with R ₂ and R ₃ , respectively, X ′ is synonymous with X, Z is hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing. Represents a heterocyclic residue, an alkyl group, or —SB—Y— (R ₄ ) (R ₅ ), M represents a divalent metal atom, R ″ represents a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group,
Represents an aryl group, a heterocyclic residue (including a condensed 5- or 6-membered unsaturated ring) or an amino group, and n _{1 to} n ₆
And m _{1 to} m ₅ each represent an integer of 1 to 6.

B represents an alkylene group having 1 to 6 carbon atoms, Y represents --N <, ═C <or --CH <, and R ₄ and R ₅ have the same meanings as R ₂ and R ₃ , respectively. However, R ₄ and R ₅ may each represent —B—SZ, and R ₂ and R ₃ , R and R ′, and R ₄ and R ₅ may be bonded to each other to form a ring.

The compound represented by the formula includes ethanolated products and salts thereof. ]

[0019]

[Chemical 13]

In the formula, Q ₁ represents a group of atoms necessary for forming a nitrogen-containing heterocycle (including a 5- or 6-membered unsaturated ring or a condensed ring), and R ₁₁ represents a hydrogen atom. , Alkali metal atom,

[0021]

Embedded image

Alternatively, it represents an alkyl group. However, Q'is Q ₁
Is synonymous with ]

[0023]

[Chemical 15]

In the formula, X ₂ is --COOM ', --H, --OH, --SO.
₃ M ', -CONH ₂ , -SO ₂ NH ₂ , -NH ₂ , -SH, -CN, -CO ₂ R
₁₆ , -SO ₂ R ₁₆ , -OR ₁₆ , -NR ₁₆ R ₁₇ , -SR ₁₆ , -SO
₃ R ₁₆ , -NHCOR ₁₆ , -NHSO ₂ R ₁₆ , -OCOR ₁₆ or -SO ₂ R ₁₆
And Y ₂ is

[0025]

Embedded image

Alternatively, it represents a hydrogen atom, and m ₉ and n ₉ each represent an integer of 1 to 10. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or

[0027]

[Chemical 17]

And R ₁₈ represents a lower alkyl group,
R ₁₉ is -NR ₂₀ R _21, represent -OR ₂₂ or -SR _22, each R ₂₀ and R ₂₁ represents a hydrogen atom or a lower alkyl radical, R
₂₂ represents an atomic group necessary for bonding with R ₁₈ to form a ring. R ₂₀ or R ₂₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation. ]

[0029]

Embedded image

In the formula, X ₁ represents a hydrogen atom or an alkali metal atom, Y ₁ represents a hydrogen atom, an alkyl group or an acyl group, R ¹ and R ² represent a hydrogen atom, an alkyl group or an allyl group,
At least one contains a sulfur atom. R ¹ and R ² may or may not be the same. m'represents an integer of 1 to 5. ] 2. 2. The solid processing agent for a silver halide photographic light-sensitive material according to 1, wherein the solid processing agent contains at least one compound selected from the general formulas [III] and [V].

3. In the above solid processing agent, the general formulas [I], [II], [III], and
3. The silver halide photographic light-sensitive material according to 1 or 2, wherein the weight ratio of the total weight of at least one compound selected from [IV] and [V] is 0.05% by weight or more and 5% by weight or less. Solid processing agent.

4. 4. The solid processing agent for silver halide photographic light-sensitive materials according to 1, 2, or 3, wherein the solid processing agent is a fixing processing agent.

5. The thiosulfate salt in the solid processing agent comprises sodium thiosulfate and / or potassium thiosulfate and ammonium thiosulfate, and the sodium thiosulfate and / or
Alternatively, the total weight of potassium thiosulfate is 2% by weight or more and 70% by weight or less, based on the total weight of the thiosulfate, for silver halide photographic light-sensitive material according to 1, 2, 3 or 4. Solid processing agent.

6. 6. The solid processing agent for silver halide photographic light-sensitive material according to 1, 2, 3, 4 or 5, wherein the solid processing agent is in the form of granules or tablets.

7. 7. The solid processing agent for silver halide photographic light-sensitive material according to 1, 2, 3, 4, 5 or 6, wherein the solid processing agent is a tablet.

The inventors of the present invention found the following facts as a result of various experiments conducted on the solid processing agent for silver halide photographic light-sensitive material.

By adding at least one compound selected from the above-mentioned general formulas [I] to [V] to the solid processing agent containing thiosulfate, the thiosulfate necessary for completing the fixing reaction is added. It is possible to reduce the amount of salt, and by reducing the amount of thiosulfate used, it is possible to suppress the sticking of thiosulfate-hydrolyzed decomposition products on the above-mentioned transfer roller portion, and to reduce the amount of photosensitive material processed per day. It is possible to have a stable fixing performance even when the processing liquid is concentrated. By using the compound of the present invention, it becomes possible to maintain stable fixing performance even if the thiosulfate concentration in the processing liquid having fixing ability varies.

At least one compound selected from the above general formulas [I] to [V] is generally known as a bleaching accelerator in the bleaching step of oxidizing to metallic silver ions formed by development. (JP-A-61-250646, etc.),
As in the present invention, it is a surprising fact that it has a fixing-promoting effect of accelerating the fixing process of solubilizing silver ions by thiosulfate, which is the next step after bleaching, and removing them from the light-sensitive material. Yes, this is a new fact obtained as a result of trial and error experiments by the present inventors.

By incorporating at least one compound selected from the above general formulas [I] to [V] into the solid processing agent, the thiosulfate can be stored even at a high temperature of 40 to 50.degree. It is possible to suppress the sulfuration of the solid processing agent, maintain the solubility of the solid processing agent in a good state, and maintain stable processing performance.

When the solid processing agent is in the form of granules or tablets, by incorporating at least one compound selected from the above general formulas [I] to [V], the solid processing agent remains solid even after long-term high temperature storage. It is also possible to suppress the degree of powder generation of the treatment agent.

The present invention will be described in detail below.

First, the compounds represented by the above general formulas [I] to [V] of the present invention will be explained.

In the above general formula [I], Q forms a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings are condensed) (eg, imidazoline ring, thiazoline ring, triazoline ring, etc.). Represents a group of atoms necessary for R ₁ , R ₁ represents a hydrogen atom, a substituted or unsubstituted 1 to 6 carbon atom alkyl group (eg, ethyl group), a cycloalkyl group (eg, cyclohexyl group), an aryl group (eg, , A phenyl group), a heterocyclic group (including those in which a 5- to 6-membered unsaturated ring is condensed) (for example, a pyridine ring group, an imidazole ring group, a thiazole ring group, etc.) or an amino group.

In the general formula [II], R ₂ and R ₃
Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, an ethyl group), a hydroxy group, a carboxy group,
Amino group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.), acyl group, aryl group (eg, phenyl group, etc.), or alkenyl group (eg, allyl group, butenyl group, etc.) Represents

[0045] A is - (C = X ') - N (R) (R'), - (CH 2) n 2 -
(C = X ′) − N (R) (R ′), − (S) m ₁ − (C = X ′) − N (R)
(R ′), − (S) m ₂ − (CH ₂ ) n ₃ − (C = X ′) − N (R) (R ′), −
(S) m ₃ − (CH ₂ ) n ₄ −N (R) (R ′), − (S) m ₄ −N (R) (R ′), −
(NH) n ₅ − (CH ₂ ) m ₅ − (NH) n ₆ − (C = X ′) − N (R) (R ′), −S
-M-S- (C = X ')-N (R) (R'), -SZ or n ₁ -valent heterocyclic residue (including those in which 5- or 6-membered unsaturated ring is condensed) (For example, a pyridine ring residue, an imidazole ring residue,
A thiazole ring residue, etc.), X represents ═S, ═O or ═NR ″, where R and R ′ have the same meanings as R ₂ and R ₃ , respectively, X ′ has the same meaning as X, Z is a hydrogen atom, Alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue (for example, pyridine ring residue, imidazole ring residue, etc.),
Represents an alkyl group (for example, a methyl group, an ethyl group, etc.) or --S--B--Y (R ₄ ) (R ₅ ), M represents an oxygen atom or a sulfur atom, and R ″ represents a hydrogen atom or a carbon atom 1. To 6 alkyl groups (eg ethyl group), cycloalkyl groups, aryl groups (eg phenyl group), heterocyclic residues (5-6
Membered unsaturated rings are also condensed) (for example, a pyridine ring residue, an imidazole ring residue, etc.) or an amino group, and n _{1 to} n ₆ and m _{1 to} m ₅ are each 1 to Represents an integer of 6.

B represents an alkylene group having 1 to 6 carbon atoms (eg, ethylene group), and Y represents --N <, = C <or --CH.
<>, And R ₄ and R ₅ have the same meanings as R ₂ and R ₃ , respectively. However, R ₄ and R ₅ may each represent —B—SZ, and R ₂ and R ₃ , R and R ′, and R ₄ and R ₅ may be bonded to each other to form a ring.

The compound represented by the general formula [II] includes ethanolated products and salts thereof.

In the general formula [III], Q ₁ is a nitrogen-containing heterocyclic ring (including a condensed 5- or 6-membered unsaturated ring)
(For example, thiazole ring, thiadiazole ring, imidazole ring, pyrimidine ring, triazole ring, pyrazine ring,
Represents a group of atoms necessary for forming a triazine ring, an oxodiazole ring, etc., and R ₁₁ is a hydrogen atom, an alkali metal atom, a group obtained by removing R ₁₁ from the general formula [III], or an alkyl group (eg, methyl group). Group, ethyl group, etc.). However,
Q'is synonymous with Q ₁ .

In the general formula [IV], X ₂ is -COOM ',
_{-H, -OH, -SO 3 M '} , - CONH 2, -SO 2 NH 2, -NH 2, -S
_{H, -CN, -CO 2 R 16} , -SO 2 R 16, -OR 16, -NR 16 R 17, -
SR _16, represents a _{-SO 3 R 16, -NHCOR 16,} -NHSO 2 R 16, -OCOR 16 or -SO ₂ R _16, Y ₂ is -S- _{[C (R 14) (R 15} ) - ] _n9 −N
(R ₁₃₎ - _{[- C (R 11) (R} 12) - ] _{m9 -, - C (= NR} 18) (R 19) or a hydrogen atom, m ₉ and n ₉ are each an integer of 1 to 10 Represents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or-[-C (R ₁₁ ) (R ₁₂ )-] _m9. represents -X _2, R ₁₈ represents a lower alkyl group (e.g., methyl group, ethyl group, etc.), R ₁₉ is -NR ₂₀ R _21, represent -OR ₂₂ or -SR _22, R ₂₀
And R ₂₁ each represent a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.), and R ₂₂ represents an atomic group necessary for forming a ring by bonding with R ₁₈ . R ₂₀ or R
₂₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation.

In the general formula [V], X ₁ is a hydrogen atom,
Represents an alkali metal, Y ₁ represents a hydrogen atom, an alkyl group (such as an ethyl group) or an acyl group, and R ¹ and R ² represent a hydrogen atom, an alkyl group (such as a methyl group or an ethyl group) or an allyl group ( At least one of the phenyl groups and the like) contains a sulfur atom. R ¹ and R ² may or may not be the same. m'represents an integer of 1 to 5.

Specific examples of the compounds represented by the general formulas [I] to [V] in the present invention are given below. However, the present invention is not limited to these.

[0052]

[Chemical 19]

[0053]

Embedded image

[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

[0059]

[Chemical formula 26]

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

Among the above compounds, compounds which are particularly preferably used from the effects of the object of the present invention are I-2, II-
6, III-9, III-10, III-13, III-31, IV-7, V
-1, V-3 and V-5 are mentioned, and particularly preferred one is the general formula [III] or [V], and the compound is II
I-10, III-13, V-3 are mentioned.

In the present invention, in order to further exert the above effects, the weight ratio of the total weight of at least one compound selected from the above general formulas [I] to [V] to the weight of thiosulfate is set. It is preferably 0.05% by weight or more and 5% by weight or less, and further 0.2% by weight or more and 2% by weight
The above is most preferable.

In the present invention, the compound of the present invention can more effectively exert the effect of suppressing the generation of powder after the solid processing agent is stored at a high temperature when the solid processing agent is for fixing.

In the present invention, the thiosulfate in the solid treating agent is used as sodium thiosulfate and / or potassium thiosulfate and ammonium thiosulfate, and the total weight of the sodium thiosulfate and / or potassium thiosulfate is the above thiosulfate. By adjusting the content of the solid treating agent in the range of 2% by weight or more based on the total weight of the salt, it is possible to suppress oxidative decomposition of thiosulfate, moisture absorption and the like due to storage of the solid treating agent under high temperature and high humidity conditions. Become.

In the present invention, the total weight of the sodium thiosulfate and / or potassium thiosulfate is more preferably adjusted to the range of 2% by weight or more and 70% by weight or less with respect to the total weight of the thiosulfate. , And more preferably 5% by weight or more and 20% by weight or less.

The solid processing agents containing thiosulfate of the present invention include solid processing agents for fixing, bleach-fixing solid processing agents, etc., but in the present invention, they are applied to all solid processing agents containing thiosulfate. To be done.

In addition to thiosulfates, known fixing agents such as sulfites, bisulfites, sulfite adducts, mesoionic compounds, thiocyanates, chelating agents, nonionic or anionic surfactants, buffers, etc. In the solid processing agent for bleach-fixing agent, a known organic acid ferric salt containing a halide, ferric aminopolycarboxylic acid salt, solid organic It may contain known bleaching components and fixing components such as acids, anti-bacterial agents and rust-preventing agents.

Further, the solid processing composition of the present invention contains at least one compound selected from polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols and saccharides to suppress decomposition of thiosulfuric acid by storage over time and The effect of preventing generation of powder of the solid processing agent due to friction after storage with time is further enhanced.

In the present invention, the polyethylene glycols are preferably compounds represented by the following general formula (I).

General formula (I) HO- (A) n ₁ ′-(B) n ₂ ′-(D) n ₃ ′ -H In the formula, A, B and D are respectively —CH ₂ CH ₂ O—, −CH ₂ CH (R) O
_{-, - CH 2 CH 2 CH} 2 O- or -CH ₂ CH (R) represents a CH ₂ O-. R represents a substituted or unsubstituted lower alkyl group (methyl group, ethyl group, propyl group, etc.) or a hydroxyl group. n ₁ ′, n ₂ ′ and n ₃ ′ each represent 0 or an integer of 1 to 500. However, the average molecular weight of this compound is preferably in the range of 2000 to 20000.

Particularly preferred exemplified compounds in the above general formula (I) are shown below.

[0074]

Embedded image

The saccharides in the present invention are monosaccharides and polysaccharides in which a plurality of these are glycosidic-bonded to each other.

The monosaccharide means a single polyhydroxyaldehyde, polyhydroxyketone and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives, and thio derivatives. Although many sugars are represented by the general formula CnH ₂ nOn, they are defined as monosaccharides in the present invention, including compounds derived from the sugar skeleton represented by this general formula. Among these monosaccharides, preferred are sugar alcohols obtained by reducing aldehyde groups and ketone groups of sugars to form primary and secondary alcohol groups, and particularly preferred is hexite having 6 carbon atoms.

Polysaccharides include celluloses, starches,
Glycogen and the like are included, and celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various decomposition products until they are hydrolyzed to maltose. Includes certain dextrins. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used in these polysaccharides are celluloses and dextrins,
More preferred are dextrins.

Specific examples of monosaccharides preferably used in the present invention are shown below.

[Exemplified Compound] B- (1) Glyceraldehyde B- (2) Dihydroxyacetone (including dimer) B- (3) D-erythrose B- (4) L-erythrose B- (5) D-Threose B- (6) L-Threose B- (7) D-Ribose B- (8) L-Ribose B- (9) D-Arabinose B- (10) L-Arabinose B- (11) D- Xylose B- (12) L-xylose B- (13) D-lyxose B- (14) L-lyxose B- (15) D-xylulose B- (16) L-xylulose B- (17) D-ribulose B -(18) L-ribulose B- (19) 2-deoxypho D-ribose B- (20) D-allose B- (21) L-allose B- (22) D-altrose B- (23) L- Altrose B- (24) D-glucose B- (25) L-glucose B- (26) D-mannose B- (27) L-ma N-Nose B- (28) D-Growth B- (29) L-Growth B- (30) D-Idose B- (31) L-Idose B- (32) D-Galactose B- (33) L-Galactose B -(34) D-talose B- (35) L-talose B- (36) D-quinobose B- (37) Digitalose B- (38) Digitoxose B- (39) Cimarose B- (40) D-sorbose B -(41) L-sorbose B- (42) D-tagatose B- (43) D-fucose B- (44) L-fucose B- (45) 2-deoxy-D-glucose B- (46) D- Psicose B- (47) D-fructose B- (48) L-fructose B- (49) L-rhamnose B- (50) D-glucosamine B- (51) D-galactosamine B- (52) D-mannosamine B -(53) D-glycero-D-galactoheptose B- (54) D-glycero-D-mannoheptose B- (55) D-glyce -L-mannoheptose B- (56) D-glycero-D-gloheptose B- (57) D-glycero-D-idoheptose B- (58) D-glycero-L-glucoheptose B- (59) D-glycero-L -Taloheptose B- (60) D-Altroheptulose B- (61) D-Mannoheptulose B- (62) D-Altro-3-heptulose B- (63) D-Glucuronate B- (64) L-Glucuronate B- (65) N-Acetyl-D-Glucosamine B- (66) Glycerin B- (67) D-Tray B- (68) L-Trait B- (69) Elitret B- (70) D -Arabite B- (71) L-Arabite B- (72) Adnit B- (73) Xylit B- (74) D-Sorbit B- (75) L-Sorbit B- (76) D-Mannit B- ( 77) L-Mannit B- (78) D- Exit B- (79) L- Exit B- (80) D- Talit B- (81) L-talit B- (82) dulcitt B- (83) allozulcit Among these exemplified compounds, B is more preferably used.
-(66) to (83), more preferably B- (74)
~ (83).

Specific examples of preferred polysaccharides used in the present invention are shown below.

C- (1) Maltose C- (2) Cellobiose C- (3) Trehalose C- (4) Gentiobiose C- (5) Isomaltose C- (6) Lactose C- (7) Raffinose C- (8) ) Genthianose C- (9) Stachyose C- (10) Xylan C- (11) Alavan C- (12) Glycogen C- (13) Dextran C- (14) Inulin C- (15) Levan C- (16) Galactan C- (17) Agarose C- (18) Amylose C- (19) Sucrose C- (20) Agarobiose C- (21) α-dextrin C- (22) β-dextrin C- (23) γ-dextrin C- (24) δ-dextrin C- (25) ε-dextrin C- (26) α-limit dextrin C- (27) β-limit dextrin C- (28) phosphorylase limit dextrin C- (29) Soluble Starch C- (30) Thin Nori Starch C- (31) White Dextrin C- (32) Yellow Dextrin C- (33) British Gum C- (34) Pine Flow (trade name, Matsutani Chemical Industry Co., Ltd. C- (35) Paindex 100 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (36) Paindex 1 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (37) Paindex 2 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (38) Pa index 3 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (39) Pa index 4 (trade name, Matsutani Chemical Co., Ltd.) C- (40) Paindex 6 (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (41) Foodtex (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (42) Max 1000 ( Product name, Matsutani Chemical Industry C- (43) Glister P (trade name, manufactured by Matsutani Chemical Co., Ltd.) C- (44) TK-16 (product name, manufactured by Matsutani Chemical Co., Ltd.) C- (45) MPD (Brand name, manufactured by Matsutani Chemical Co., Ltd.) C- (46) H-PDX (Brand name, manufactured by Matsutani Chemical Co., Ltd.) C- (47) Stacodex (Brand name, manufactured by Matsutani Chemical Co., Ltd.) ) C- (48) Mabit (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (49) Pullulan (trade name, manufactured by Hayashibara Shoji Co., Ltd.) C- (50) Methylcellulose C- (51) Dimethylcellulose C- (52 ) Trimethyl cellulose C- (53) Ethyl cellulose C- (54) Diethyl cellulose C- (55) Triethyl cellulose C- (56) Carboxymethyl cellulose C- (57) Carboxyethyl cellulose C- (58) Aminoethyl Cellulose C- (59) Hydroxymethylcellulose C- (60) Hydroxyethylmethylcellulose C- (61) Hydroxypropylcellulose C- (62) Hydroxypropylmethylcellulose C- (63) Hydroxypropylmethylcellulose acetate succinate C- (64) Carboxymethyl Hydroxyethyl Cellulose Among these exemplified compounds, more preferably used are C- (21) to (64), and more preferably C- (21).
~ (48).

In the present invention, the addition amount of these saccharides is 0.5% (W / W) per unit weight of the solid developing agent for color development.
~ 30% (W / W) is preferred, more preferably 1.0%
(W / W) to 20% (W / W).

Sugars are widely present in nature, and commercial products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation or dehydration reaction.

The above-mentioned compounds represented by the general formula (I), polyvinylpyrrolidones, polyvinyl alcohols and saccharides may be used in the form of powdery raw materials or mixed in a granulated state, or The effect of the present invention can be exhibited even when used in the state of being granulated with the thiosulfate of the present invention.

In the present invention, by containing a sulfite and a pyrosulfite, it becomes possible to further prevent the above-mentioned sulfide generation and prevent the generation of powder after the solid processing agent is stored at high temperature. Examples of the sulfite and pyrosulfite include ammonium salt, sodium salt and potassium salt, and it is preferable to use sodium salt and potassium salt from the viewpoint of the effect of the present invention.

[0086]

EXAMPLES The present invention will be described below with reference to examples. However, the embodiment of the present invention is not limited to these.

Example 1 The replenishing device section of the color negative film processor CL-KP-50QA was modified as shown in FIG. 1, and the solid processing agent replenishing device shown in FIG. 2 was used. After Konica Color Super DD400 film was imagewise exposed, a columnar container containing tablets was set in the tablet charging section for processing.

FIG. 1 shows a solid processing agent replenishing device 2A of the present invention.
2B, 2C, 2D is a diagram showing the mounting position where the KP-50QA (automating machine A) is mounted. FIG.
A, 2B, 2C and 2D are color developing tank 1A and bleaching tank 1, respectively.
B, the fixing tank 1C, and the stabilizing tank 1D are attached at the positions shown by the diagonal lines above. FIG. 2 is a block diagram showing an embodiment of the solid processing agent replenishing (charging) devices 2A, 2B, 2C, and 2D. Dissolution chambers 106 for charging the solid processing agent 111 are provided at the sides of each tank. .

In FIG. 2, a solid processing agent (hereinafter also referred to as a tablet or a tablet chemical) 111 is housed in a container (cartridge) 101 divided into a plurality of chambers and sealed by a slide type cap 102. When this cartridge is set on the cartridge support base 103 of the solid processing agent automatic feeder installed at the upper part of the processing tank of the automatic processor, the cap 102 is opened, and the tablet is rotated from the obliquely fixed cartridge to the rotating cylinder. It rolls into the slit 105 of 104.
The cutouts 105 of the rotating cylinder 104 are cut differently from each other so that a plurality of tablets stored in different rooms in the cartridge cannot roll down at the same time.

Depending on the amount of processing of the photosensitive material, the rotating cylinder 104
However, it rotates, and at the same time, the shutter 108 opens and tablets are placed in the filter tank (or dissolution tank) 106 that is attached to the processing tank.
It is put in locks one by one. 107 is a filter.

The processing steps are shown below.

Treatment process Treatment time Treatment temperature Replenishment water amount (ml / m ² ) Color development 3 minutes 15 seconds 38.0 ° C 520 Bleach 45 seconds 38.0 ° C 100 Fixing-1 45 seconds 38.0 ° C Fixing-2 45 seconds 38.0 ° C Table 1 Description Stable -1 20 seconds 38.0 ° C Stable-2 20 seconds 38.0 ° C Stable -3 20 seconds 38.0 ° C 860 Dry 80 seconds 55 ° C Fixing from 2 to 1, stable from 3 to 2, 2 to 1 countercurrent The bleaching tank was aerated with an air pump.

The tank liquid at the start was prepared by using a replenisher of Konica Color Negative Film treating agent CNK-4-52 and a starter.

Next, the following color negative treating agent was prepared.

1) Color development replenishing tablet operation for color negative film (1) Developing agent CD-4 [4-amino3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 60 g In a commercially available hammer mill Grind until the average particle size reaches 10 μm. This fine powder was granulated by adding 10 ml of water at room temperature for about 7 minutes in a commercial stirred granulator, and the granulated product was then dried in a fluid bed dryer.
The granules were dried at 40 ° C. for 2 hours to almost completely remove the water content to prepare granules (A) for color developing replenishment for color negative.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in the operation (1), and then mixed and granulated. The amount of water added was 3.5 ml, and after granulation, it was dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product to prepare granules (B) for color development replenishment for color negative.

Operation (3) 1-Hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8 g, potassium carbonate 350 g, sodium hydrogen carbonate 3 g, sodium bromide 3.7 g and mannite 22 g polyethylene glycol 6000 5.0 g are crushed and mixed in the same manner as in steps (1) and (2), and water is added. Quantity 40
Granulate to ml. After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product to prepare color developing replenishing granules (C) for color negative.

Granules (A) to (C) for color development replenishment for color negative described above are mixed, and 2 g of sodium N-myristoylalanine is added to the granules thus prepared, and the mixture is kept at 25 ° C. and 40% RH or less. Mix evenly for 10 minutes using a mixer in a conditioned room. Next, mix the mixture with Kikusui Seisakusho KK
Using a tableting machine modified from Tough Press To Correct 1527HU, compression filling was performed at a filling amount of 10 g per tablet to prepare a color developing replenishing tablet for a color negative having a diameter of 30 mm.

2) Bleaching Replenishing Tablet for Color Negative Operation (4) 1,3-Propanediamine 4 Ferric Ammonium Ferric Acid Monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g, and Pine Flow (Matsuya Chemical Co., Ltd.) 17 g were pulverized and mixed in the same manner as in the operation (1), and the amount of water added was 8 ml to perform granulation. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (5) 133 g of succinic acid, 200 g of ammonium bromide and pine flow
10.2 g is crushed, mixed and granulated in the same manner as in the operation (1). The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water.

Operation (6) In the same manner as in the operation (1), 66.7 g of potassium sulfate, 60 g of potassium hydrogencarbonate and 8 g of mannite are pulverized, mixed and granulated. The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water.

The granules prepared by the above operations (4) to (6) are uniformly mixed for 10 minutes using a mixer in a room where the humidity is controlled to 25 ° C. and 40% RH or less. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and they are mixed for 3 minutes. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 10 g per tablet to give a color negative bleaching tablet having a diameter of 30 mm and a thickness of 10 mm. did.

3) Fixing replenishing tablet for color negative operation (7) sodium thiosulfate / ammonium thiosulfate = 250 g / 2
250 g, sodium sulfite 180 g, potassium carbonate 20 g, ethylenediamine tetraacetic acid disodium salt 20 g, pine flow (Matsuya Chemical Co., Ltd.) 70 g, and the compound 25 g shown in Table 1 were ground in a commercially available bandam mill to an average particle size of 30 μm, and this powder 50 ml of water is added in a stirring granulator for about 10 minutes at room temperature to granulate. After granulation, the granulated product is heated in a fluidized bed dryer at 60 ° C for 120
Dry for minutes to remove almost completely the water of the granulate. Next, the dried granules were made to have an average particle size of 800 μm so that 50% or more of the particles were within a deviation of ± 200 to ± 250 μm.

Operation (8) 30 g of N-lauroyl sarcosine sodium is mixed with the fixing replenishing granules in a room conditioned at 25 ° C. and 45% RH or less for 5 minutes using a mixer. Then mix the mixture with Kikusui
A tableting machine modified from Tough Pressed Collect 1527HU manufactured by Co., Ltd. was used to make a filling amount of 10 g, and tablets each having a diameter of 30 mm and a thickness of 10 mm were prepared.

4) Stable replenishing tablet operation for color negative (9) 200 g of m-hydroxybenzaldehyde (hereinafter sometimes abbreviated as mHBA) and 21 g of lithium hydroxide monohydrate 21 g in an air jet fine pulverizer It was ground to 10 μm.

Further, the mixture was uniformly mixed for 10 minutes by using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less to obtain a ground mixture.

Operation (10) The above ground mixture was granulated by spraying 3.0 ml of water at room temperature for about 7 minutes in a commercially available fluidized bed spray granulator, and then dried at 45 ° C. for 8 hours. . Then granulate in vacuum
The granulated product was dried at 2 ° C. for 2 hours until the water content of the granulated product was reduced to 0.1 to 0.3% by weight to obtain a granulated product. The granulated product had a particle size of 300 to 600 μm and a bulk density of 0.8 g / cm ³ .

Operation (11) Further, the above granulated product was toughly pressed and collected by Kikusui Seisakusho.
The filling amount per tablet is 9.
The tablet was compressed to 0 g to give a stable negative tablet for color negative having a diameter of 30 mm. The bulk density of this tablet is 1.7g
It was / cm ³ .

The color development replenishing tablets, each of which is a 135 size 24 piece film, is 7.1 pieces, the bleaching replenishing tablet is 3.6 pieces, and the stable replenishing tablet is 125 pieces.

Under the above-mentioned treating agents and treating conditions, a negative film treatment amount per day was set to 0.5 m ^{2 and} a running experiment was carried out for 3 weeks. After the running experiment, an unexposed light-sensitive material sample was treated to determine the amount of residual silver. It was measured by the X-ray method.

The first tank of fixing after the running experiment, 2
The treated solution in the tank was stored at 5 ° C for 1 week, and the appearance of the stored solution was visually observed. The evaluation criteria are shown below.

⊚: There is no crystal precipitate and there is no problem. ◯: Floating matter is slightly observed, but there is no problem. ×: Large crystals of thiosulfate are produced and liquid circulation by a pump. It is a level that causes problems.

After the running experiment, the light-sensitive material samples were processed and visually evaluated for scratches and stains on the surface of the samples and for the appearance of the transition roller in the fixing tank.

X: A large amount of sulfide was deposited on the transfer roller, and scratches were confirmed on the surface of the treated sample. ◯: There were few precipitates on the transfer roller, and the treated sample was at a level without problems. .

The results are shown in Table 1.

The thiosulfate concentration in the fixer after running in the table is the result of analysis of the thiothiosulfate concentration in the second fixing bath after the running experiment by reverse iodometric titration.

[0117]

[Table 1]

As is clear from Table 1, by using the compound of the present invention, the fixing performance can be maintained even when the concentration of thiosulfate in the fixing processing solution is reduced, and the low temperature storage of the processing solution is possible. It can be seen that it is possible to prevent scratches and stains from adhering to the surface of the photosensitive material due to crystal precipitation and crystal precipitation of the transfer roller of the fixing tank.

Example 2 The replenishing system of the fixing solid processing agent was changed as shown below, and the additives to be used, the amount of replenishing water in the fixing step, and the interval for feeding the solid processing agent were changed as shown in Table 2. The same experiment and evaluation as in Example 1 were performed. Table 2 shows the results.

Here, the replenishing method of the fixing solid processing agent will be described.

(Powder method) Fixing replenishing powder: sodium thiosulfate / ammonium thiosulfate = 250 g
/ 2250g, sodium sulfite 180g, potassium carbonate 20g, ethylenediamine tetraacetic acid disodium salt 20
g and Pine Flow (Matsuya Chemical Co., Ltd.) 70 g, and the compound 20 g shown in Table 2 in a commercially available bandam mill with an average particle size of 30 μm.
The mixture is pulverized and mixed until it becomes a powder for fixing replenishment.

The feeding device of FIG. 2 used in Example 1 was changed to FIG.

FIG. 3 is a cross-sectional view showing still another supply device for the solid processing agent, which can be used for granular and powder solid processing agents. The supplying device 70 puts a granular or powder processing agent into a hopper 71 and then a piston 75 depending on the processing amount of the photosensitive material.
Moves in the horizontal direction (to the right) and a fixed amount of the granular processing agent or powder processing agent enters the measuring hole 72, and the piston 75 moves in the opposite horizontal direction (to the left) and the discharging portion 74 causes the fixed amount of the granular processing agent or powder. Is supplied to the filter tank. The powder unit supply amount by the supply device of FIG. 3 was adjusted to be 10 g.

(Granule Method) The standing material obtained by the operation (7) described in Example 1 was used as fixing replenishing granules.

Fixing Replenishing Granule Feeding Device The feeding device of FIG. 2 used in Example 1 was changed to FIG. The supply device shown in FIG. 3 was adjusted so that the amount of granules supplied according to FIG. 3 was 10 g.

(Tablet system) The same tablet and feeder as in Example 1 were used.

[0127]

[Table 2]

As is clear from Table 2, by using the compound of the present invention, the fixing performance can be maintained even when the concentration of thiosulfate in the fixing processing solution is reduced, and at the time of storing the processing solution at a low temperature. It is possible to maintain the crystal precipitation and fixing performance of the above, and to prevent scratches, stains, and adhesion on the surface of the photosensitive material due to crystal precipitation during low temperature storage of the processing solution and crystal precipitation at the crossover roller of the fixing tank. I understand.

Example 3 A fixing replenishing solid processing agent for a color film was prepared according to the following procedure.

(I) Fixing replenishing granular processing agent sodium thiosulfate / ammonium thiosulfate = 250 g / 2
250 g, sodium sulfite 180 g, potassium carbonate 20 g, ethylenediamine tetraacetic acid disodium salt 20 g, Pine Flow (Matsuya Chemical Co., Ltd.) 70 g, and the compound 20 g shown in Table 3 were ground in a commercially available bandam mill to an average particle size of 30 μm, and this powder 50 ml of water is added in a stirring granulator for about 10 minutes at room temperature to granulate. After granulation, the granulated product is heated in a fluidized bed dryer at 60 ° C for 120
Dry for minutes to remove almost completely the water of the granulate. Next, the dried granules were made to have an average particle size of 800 μm so that 50% or more of the particles were within a deviation of ± 200 to ± 250 μm.

(II) Fixing Replenishing Tablets The above fixing replenishing granular processing agent was mixed with 30 g of N-lauroylsarcosine sodium for 30 minutes at 25 ° C. and 45% RH or less in a room with a mixer for 5 minutes. . Then, the mixture was made to have a filling amount of 10 g by a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho KK, and tablets having a diameter of 30 mm and a thickness of 10 mm were prepared.

30 g of each of the powder and the granular treating agent was divided into 3 tablets, and each tablet was divided into 3 tablets, placed in a high density polyethylene (HDPE) bag (10 × 10 cm) and sealed.
Store at ℃, 50% RH for 1 month. After adding water to the granules and tablets (3 tablets) after storage to make 100 cc and stirring well, visually observe these aqueous solutions and then filter to determine the S ₂ O ₃ ² -salt concentration during filtration. It was analyzed by reverse iodometric titration.

Further, the granular processing agent stored at 50 ° C. and 50% RH for 1 month was taken out from the polyethylene bag and sieved to remove particles having a particle size of 149 μm or less. The weight of is measured. Next, this granular treatment agent was put in a polyethylene bag again and sealed, and then I
A vibration test (test condition: 5 to 67 Hz cycle, 5 minutes for 24 sets, 120 minutes) was performed using a vibration tester BF-UA manufactured by DEX, and the solid treatment agent after the vibration test was sieved again to obtain particles of 149 μm or less. The diameter of the solid treating agent was removed, the weight of the remaining solid treating agent was measured, and the degree of powder generation of the solid treating agent after storage was evaluated by the following formula. The tablet treatment agent was stored for 1 month in an environment of 50 ° C. and 50% RH, and then the degree of powder generation was evaluated by the above method.

[0134]

[Equation 1]

The evaluation criteria for the state of the liquid dissolved after the solid processing agent was stored at high temperature and the powder generation degree after the solid processing agent was stored at high temperature are shown below.

(Appearance of liquid dissolved after storage at high temperature) ⊚: No precipitate or floating matter is observed at all ◯: No precipitate is observed at all XX: A large amount of insoluble matter is floating on the liquid surface (high) Degree of powder generation after storage under wet conditions) ◎ ◎ ◎: 0.2% or less ◎ ◎: 0.2 to 0.5% ◎: 0.5 to 1.0% ○: 1.0 to 2.0% ×: 2 to 4% × ×: 4 to 6% 3 shows.

[0137]

[Table 3]

As is clear from Table 3, the application of the compound of the present invention suppresses the formation of insoluble matter due to the decomposition of S ₂ O ₃ ^2- during the high temperature long-term storage of the solid replenishing agent for fixing replenishment, and It can be seen that it is possible to suppress the solubility and deterioration of the treatment agent and the generation of powder of the solid treatment agent.

Example 4 A bleach-fixing solid processing agent for color paper was prepared according to the following procedure.

(I) Granular processing agent for bleach-fixing (12) Diethylenetriamine pentaacetic acid ferric ammonium salt 720
g, 70 g of diethylenetriamine pentaacetic acid, and 80 g of Pine Flow (Matsuya Chemical Co., Ltd.) were pulverized in a commercially available bandam mill, and 30 ml of this powder was added in a stirring granulator at room temperature for about 10 minutes for granulation. After granulation, the granules are dried for 2 hours at 60 ° C to remove almost all the water content, and the granules have an average particle size of 800 μm.
More than 50% of the particles were allowed to fall within a deviation of ± 200 to ± 250 μm.

Operation (13) 800 g of thiosulfate (described in Table 3), 160 of sodium sulfite
g, 60 g of sodium bisulfite and 60 g of Pine Flow (Matsuya Chemical Co., Ltd.) were added, and pulverized and mixed in the same manner as in the operation (1) to granulate. The amount of water added was 40 ml, and after granulation, 120 at 60 ° C
The granules are dried for a minute to almost completely remove the water content, and the granules have an average particle size of 800 μm.
The deviation was within ± 250 μm.

Next, the granules obtained in the operations (12) and (13) were combined and mixed in a room where the humidity was adjusted to 25 ° C. and 40% RH using a mixer to obtain bleach-fixing granules. .

(II) Tablet for bleach-fixing 30 g of N-lauroylsarcosine sodium was mixed with the above-mentioned granular processing agent for bleach-fixing in a room conditioned at 25 ° C. and 45% RH or less for 5 minutes using a mixer. . Then, the mixture was made to have a filling amount of 10 g by a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho KK, and tablets having a diameter of 30 mm and a thickness of 10 mm were prepared.

30 g of each of the granular treatment agents was divided, and the tablets were divided into 3 tablets, and the same experiment and evaluation as in Example 3 were carried out. The results are shown in Table 4.

[0145]

[Table 4]

As is clear from Table 4, by applying the compound of the present invention, the formation of insoluble matter due to the decomposition of S ₂ O ₃ ^2- during the high temperature long-term storage of the fixing replenishing group treating agent is suppressed, and It can be seen that it is possible to suppress the solubility and deterioration of the treatment agent and the generation of powder of the solid treatment agent.

Example 5 Example 1 was repeated, except that the amount of replenishing water in the fixing step, the interval for adding the solid processing agent, and the weight of the additive of the present invention in the solid processing agent / weight of thiosulfate were changed as shown in Table 5. The same experiment and evaluation were performed. The results are shown in Table 5.

[0148]

[Table 5]

As is apparent from Table 5, by using the compound of the present invention and adjusting the weight of the compound of the present invention in the solid processing agent / the weight of thiosulfate to the range of the present invention, Fixing performance can be maintained even when the thiosulfate concentration is reduced, and scratches, stains, and adhesion on the surface of the photosensitive material due to crystal precipitation during low temperature storage in the processing solution and crystal precipitation at the crossover roller of the fixing tank. It can be seen that it is possible to prevent

Example 6 Table 6 shows the amount of replenishing water in the fixing step, the interval for adding the solid processing agent, and the weight of sodium thiosulfate / total thiosulfate in the solid processing agent.
Change as shown in, and place the fixing replenishment tablet used in Example 1 in a bag of high density polyethylene (HDPE),
The same experiment and evaluation as in Example 1 were carried out except that the running experiment was started after storage for 2 weeks in the environment of ° C and 80% RH.

[0151]

[Table 6]

As is clear from Table 6, stable solids were prepared by using the compounds of the present invention and further adjusting the weight ratio of sodium thiosulfate of the present invention / total thiosulfate weight of the present invention in the solid treating agent to the range of the present invention. The preservability of the processing agent can be maintained and the fixing performance can be maintained even when the concentration of thiosulfate in the fixing processing solution is reduced, and the precipitation of crystals during storage at low temperature in the processing solution and the crossover roller of the fixing tank can be maintained. It can be seen that it is possible to prevent scratches, stains, and adhesion on the surface of the photosensitive material due to crystal precipitation.

[0153]

The solid processing agent for silver halide photographic light-sensitive materials according to the present invention prevents sticking phenomenon at the transition roller portion,
Even when the amount of photosensitive material processed per day is small,
Stable fixing processing performance can be maintained and good storability can be obtained even under high temperature long-term storage conditions.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing a mounting position of a solid processing agent replenishing device to an automatic developing machine.

FIG. 2 is a configuration diagram of an example of a solid processing agent supply (input) device,
It is explanatory drawing of a rotating cylinder, and a perspective view of a slide-type cap and a cartridge (discharging part). It is a mechanism diagram of a solid processing agent charging device.

FIG. 3 is a cross-sectional view of a granular and powder processing agent supply device.

[Explanation of symbols]

 1 Solid Processing Agent 1A to 1D Processing Tank 2A, 2B, 2C, 2D Solid Processing Agent Replenishing Device 101 Cartridge 102 Sliding Cap 103 Cartridge Support 104 Rotating Cylinder 105 Notch Port 106 Filter Tank 107 Filter 108 Shutter 109 Processing Tank 110 Canopies 111 Solid processing agents (tablets)

Claims (7)

[Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material, which is directly supplied to a processing solution for a silver halide photographic light-sensitive material having a fixing ability, containing a thiosulfate and having the following general formula [I]: A solid processing agent for silver halide photographic light-sensitive materials, comprising at least one compound selected from [II], [III], [IV] and [V]. Embedded image [In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. It represents 6 substituted or unsubstituted alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (including those in which 5 to 6-membered unsaturated rings are condensed), or amino groups. ] [Chemical 2] [In the formula, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group; Represent A is Or an n ₁ -valent heterocyclic residue (including a condensed 5- or 6-membered unsaturated ring), X is ═S, ═O or ═N
Represents R ″, where R and R ′ are synonymous with R ₂ and R ₃ , respectively, X ′ is synonymous with X, Z is hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue , An alkyl group, or —S—B—Y— (R ₄ ) (R ₅ ), M represents a divalent metal atom, R ″ represents a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group,
Represents an aryl group, a heterocyclic residue (including a condensed 5- or 6-membered unsaturated ring) or an amino group, and n _{1 to} n ₆
And m _{1 to} m ₅ each represent an integer of 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms, Y is -N <, = C <or represents -CH <, R ₄ and R ₅ have the same meanings as R ₂ and R _3, respectively. However, R ₄ and R ₅ may each represent —B—SZ, and R ₂ and R ₃ , R and R ′, and R ₄ and R ₅ may be bonded to each other to form a ring. The compound represented by the formula also includes an ethanol compound and a salt thereof. ] [Chemical 4] [In the formula, Q ₁ represents an atomic group necessary for forming a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring or a saturated ring), and R ₁₁ represents a hydrogen atom or an alkali. Metal atom, Or represents an alkyl group. However, Q'is synonymous with Q ₁ . ] [Chemical 6] [In the formula, X ₂ is -COOM ', -H, -OH, -SO ₃ M', -CONH
₂ , -SO ₂ NH ₂ , -NH ₂ , -SH, -CN, -CO ₂ R ₁₆ , -SO
₂ R ₁₆ , -OR ₁₆ , -NR ₁₆ R ₁₇ , -SR ₁₆ , -SO ₃ R ₁₆ , -NHCOR
₁₆ , —NHSO ₂ R ₁₆ , —OCOR ₁₆ or —SO ₂ R ₁₆ and Y ₂ is Alternatively, it represents a hydrogen atom, and m ₉ and n ₉ each represent an integer of 1 to 10. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇
And R ₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or R ₁₈ represents a lower alkyl group, R ₁₉ represents —NR ₂₀
R _21, represents -OR ₂₂ or -SR _22, each R ₂₀ and R ₂₁ represents a hydrogen atom or a lower alkyl group, R ₂₂ represents an atomic group necessary to form a ring with R ₁₈ . R ₂₀ or R ₂₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation. ] [Chemical 9] [In the formula, X ₁ represents a hydrogen atom or an alkali metal atom, and Y ₁
Represents a hydrogen atom, an alkyl group or an acyl group, and R ¹ and R ² represent a hydrogen atom, an alkyl group or an allyl group, at least one of which contains a sulfur atom. R ¹ and R ² may or may not be the same. m'represents an integer of 1 to 5. ] 2. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent contains at least one compound selected from the general formulas [III] and [V]. Agent. 3. In the solid processing agent, the compounds represented by the general formulas [I], [II], [III] and [I] with respect to the weight of thiosulfate.
3. The silver halide photographic light-sensitive material according to claim 1, wherein the total weight ratio of at least one compound selected from V] and [V] is 0.05% by weight or more and 5% by weight or less. Solid processing chemicals. 4. The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a fixing processing agent. 5. The thiosulfate salt in the solid treating agent comprises sodium thiosulfate and / or potassium thiosulfate and ammonium thiosulfate, and the total weight of the sodium thiosulfate and / or potassium thiosulfate is the total amount of the thiosulfate salt. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, 2, 3 or 4, wherein the content is 2% by weight or more and 70% by weight or less based on the weight. 6. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, 2, 3, 4, or 5, wherein the solid processing agent is in the form of granules or tablets. 7. The solid processing agent for silver halide photographic light-sensitive materials according to claim 1, 2, 3, 4, 5 or 6, wherein the solid processing agent is a tablet.